Stabilized solutions of metal-or-ganic compounds and method of making the same



STABILIZED SOLUTIONS OF METAL-OR- GANIC COMPOUNDS AND METHOD OF MAKING THE SAME Willard E. Lyons, Chicago, Ill., assignor to Leo Corpsoration, Chicago, Ill., a corporation lllino No Drawing. Application May 7, 1937,

Serial No. 141,255

12 Claims.

This invention relates to stabilized, solutions of metal-organic compounds and to a method of making the same. More particularly the invention relates to the stabilization of motor fuels wherein the stabilizing agent is an acid reacting substance soluble in water but relatively insoluble in the liquid hydrocarbons.

Other and further important objects of this comprising liquid hydrocarbons containing disinvention will become apparent from the followsolved metal organic compounds, by the addition ing description and appended claims. thereto of acid reacting substances soluble in The liquid hydrocarbons to-which my invenwater but relatively insoluble in the liquid hytion is particularly directed are those generally drocarbons. employed as motor fuels, such as gasoline,benm Metal organic compolmds, for instance the zene, polymerized hydrocarbons, or blends thereheavy metal compounds of beta diketones, are of. Of the metal organic compounds which may susceptible to hydration or hydrolysis when water be added to such hydrocarbons for increasing the is present. This is true when such compounds are efliciency of their combustion in internal combusdissolved in liquid hydrocarbons, such as gasoline tion engines, the heavy metal compounds of the and the like, as in the manufacture of anti-knock beta diketones have been found particularly use- 15 motor fuels, for the reason that minor propor-' ful. The metals intended to be included by the tions of water are almost invariably associated term heavy metals are those classified in the with the liquid hydrocarbons. Water, for examperiodic table shown in Demings General Chemple, finds its way into receptacles containing istry, fourth edition. These compounds, while motor fuels by virtue of the breathing action forming relatively s l lu i n n liq hyso that takes place, the moisture introduced with drocarbons that are free from water, have a the air into the receptacle being condensed quite tendency to form insoluble precipitates when largely around the walls and accumulating at the water is present, due probably to hydrolysis or bottom of the receptacle. Also, due to the very hydration with the consequent formation of basic slight solubility of water in gasoline, a very minor salts of the compounds or bases of the metal. 25 proportion of water may be dispersed in the body In accordance with the method of this invenof gasoline delivered for use as the motor fuel. tion, an acid reacting substance, which is water I have now found that the tendency of metallic soluble but relatively insoluble in liquid hydrocarcompounds to become hydrolyzed or hydrated, bons, is added to the solution of the heavy metal 3 due to the presence of water in motor fuels or in Organic co pounds in the liquid hydrocarbons. 80 the receptacles in which the motor fuels are Various acid reacting substances can be used for stored, may be inhibited by the addition to the this purpose, s h as boric acid. phosphoric acid. water phase of an acid reacting substance capable water soluble acid metal salts like sodium bisulof furnishing a suflicient hydrogen ion con ntraphate, water soluble organic acids, such as acetic,

tion to retard or even prevent such action from citric, sal cyl .D D y 0 y p op onic, lac- 35 taking place, In the absence of such inhibiting tic, saccharic, formic, malic, malonic, maleic, taraction, the water present would t d t cause taric, succinic and various acidic compounds hydrolysis or hydration of the metal organic comwh ch can form water Soluble salts. pounds with the formation of basic salts or bases If the ac reacting Substance 0 b added to of the metal which are insoluble both in the motor the liquid hydrocarbons solution is relatively in- 40 fuel and in the water present. The addition to Soluble in the hydrocarbons and has a spec fic the water, however, of acid reactive substances v ty g e er a a Of t e hyd ca bons. in accordance with/this invention prevents such the acid reactin Substance. W added to a tank precipitation of metal bearing substances over a o o h r r ep l containing the hydro rbon substantial period of time. will sink to the bottom by gravity and will accum- 45 It is therefore an important object of this inla e th re in any wa r th m y be present or vention to provide a method of stabilizing solua y Subsequently form d o t in t e tions of metal organic compounds in liquid hytom. In thi m n r. lar st r nks. drocarbons where water is present or is likely to nk c r n other r p s f r liq hy obecome associated with the liquid hydrocarbons. carbons y have their contents protected 50 It is a further important object of this invenagainst the hydrolyzin hydrating a on o tion to provide a method of stabilizing motor fuels y W te that y e e pr e t a the tim having dissolved'therein compounds of beta dikeof treatment or that may subseque y m tones with heavy metals where such compounds e during the storage p are susceptible to hydrolysis or hydration in the The amount of inhibitor to be added to any 55 presence of water. Y given mass of liquid hydrocarbons, gasoline or It is a further important object of this inventhe-like, will depend upon the amount of water tion to provide a stabilized solution of heavy present in association with the hydrocarbons, or metal compounds of beta diketones in liquid hythe amount of water that may reasonably be so drocarbons, such as motor fuels and the like, expected to collect during the storage period. 50

In general, it is sumcient ii the acid reacting substance is added to the receptacle containing liquid hydrocarbons in an amount capable of furnishing a pH numerically less than that at which the heavy metal organic compound tends to be'g'in'to form an insoluble precipitate. Since an excess of the inhibitor is not of itself harmful, unless carried over mechanically with the liquid hydrocarbons, no particular care need be taken in guarding against the use of an excess of the inhibitor.

The following examples will serve to illustrate preferred embodiments of this invention as applied to the treatment of motor fuels containing heavy metal compounds of beta diketones:

Example N0. 1

Gasoline treated with a heavy metal beta diketone in an amount of from 0.0001% by welght and upwards is contained within a large storage tank. The amount of water present in the bottom is estimated at 10 lbs. Sufllcient dry boric acid is added through the top of the tank to form a saturated boric acid solution with the estimated amount of water and leave an excess of boric acid for any water that may later accumulate during the expected continued length of storage of the gasoline. About 0.5 lb. of boric acid might thus be added, but as little as 0.1 lb. would be immediately suiiicient. The pH of the resulting boric acid solution is in the neighborhood of 5.6, which is sufficient to inhibit or prevent the hydrolysis or hydration of the heavy metal beta diketone present in the gasoline.

Example No. 2

With the same conditions as recited in Example No. l, in place of boric acid, about lb. of ortho-phosphoric acid is added. Being of greater density, the phosphoric acid settles through the body of the gasoline and dissolves in the water present at the bottom of the tank.

Example N0. 3

With the same conditions as specified in Example No. '1, in place of-boric acid, about 2 lbs. of lactic acid are added.

Other acids or acid reacting substances may be similarly used in amounts suflicient to produce a water solution having a pH equal to or numerically less than about 5.6.

In the foregoing examples, the heavy metal beta diketone compounds may be the acetylacetonates, propionyacetonates, or mixtures thereof,

of any one or more of the following heavy metals:

Cobalt Zirconium Nickel Beryllium Iron 7 Platinum Manganese Palladium Copper Thorium Lead Chromium Uranium Aluminum Molybdenum Rare earth metals such Vanadium as cerium, etc.

It will be understood, however, that other organic compounds of any of the heavy metals, which are soluble in liquid hydrocarbons and which have a tendency to hydrolyze or become hydrated in the presence of water may be present instead of, or in admixture with, a beta diketone compound, and that the liquid hydrocarbon solutions thereof may be stabilized in the manner hereinabove described.

In general, the organic part of the compound requiring stabilization, may be any organic acid or compound reacting as an acid to combine with a metal. Examples of such organic acids or acid reacting organic compounds are:

Naphthenic and paraiiinic acids Mono alkyl esters of salicylic, phthalic, camphoric, malonic and other dicarboxylic organic acids Cresylic acid and other phenols Mercaptans Aceto acetic acid esters and their homologues Long chain saturated and unsaturated fatty acids Aryl carboxylic acids I am aware that numerous details of the process may be varied through a wide range without departing from the principles of this invention, and I, therefore, do not purpose limiting the patent granted hereon otherwise than necessitated by the prior art.

I claim as my invention:

1. The method of stabilizing a solution of a metal beta diketone in gasoline in the presence of a water phase, which comprises incorporating a gasoline insoluble, but water soluble substance into said water phase to furnish hydrogen ions in an amount sufilcient to inhibit the hydrolysis and hydration of said metal beta diketone compound.

2. The method of stabilizing a solution of a metal beta diketone in gasoline in the presence of a water phase, which comprises incorporating boric acid into said water phase to furnish hydrogen ions in an amount suiiicient to inhibit the hydrolysis and hydration of said metal beta diketone compound.

3. The method of stabilizing a solution of a beta diketone compound of a heavy metal in liquid hydrocarbons in the presence of a water phase, which comprises incorporating a gasoline insoluble, but water soluble substance into said water phase to furnish hydrogen ions in an amount sufiicient to inhibit the hydrolysis and hydration of said metal beta diketone compound. 4. The method of stabilizing a solution of a beta diketone compound of a heavy metal in a hydrocarbon motor fuel when in the presence of a water phase, which comprises dissolving in said water phase an acid reacting compound which is relatively insoluble in the motor fuel and which in water solution provides a pH value which is numerically less than 5.6.

5. The method of stabilizing a solution of a beta diketone compound of a heavy metal in a liquid hydrocarbon that is in physical contact with water, said compound being susceptible to hydrolysis or hydration, which method comprises increasing the hydrogen ion concentration of the water present to a point at which hydrolysis and hydration of said compound is inhibited by the addition to said water of a hydrogen ion furnishing substance relatively insoluble in said hydrocarbon.

6. The method of stabilizing a solution of a beta diketone compound of a heavy metal in a liquid hydrocarbon that is in physical contact with water, said compound being susceptible to hydrolysis or hydration, which method comprises increasing the hydrogen ion concentration of the water present to a point at which hydrolysis and hydration of said compound is inhibited by the addition of boric acid to said water.

7. The method of stabilizing a solution of a M M... I

beta diketone compound of a heavy metal in a liquid hydrocarbon that is in physical contact hydration of said compound is inhibited by the addition of phosphoric acid to said water.

'8. The method of stabilizing a solution of a beta diketone compound of a heavy metal in a liquid hydrocarbon that is in physical contact with water, said compound being susceptible to hydrolysis or hydration, which method comprises increasing the hydrogen ion concentration of the water present to a point at which hydrolysis and hydration of said compound is inhibited by the addition of lactic acid to said water.

9. A stabilized storage system of a liquid hydrocarbon motor fuel containing a heavy metal beta diketone compound having a tendency to precipitate therefrom in the presence of water, said system comprising a liquid hydrocarbon phase containing a heavy metal beta diketone compound dissolved therein, and a relatively immiscible aqueous phase in direct contact with said first phase having dissolved therein an acid reacting substance insoluble in said first phase, said acid reacting substance furnishing solely by virtue of dissociation due to solution a sufiicient stable hydrogen ion concentration at the interface between said phases to inhibit said tendency of said heavy metal organic compound to precipitate.

10. A stabilized storage system as defined in claim 9, wherein the acid'reacting substance is boric acid.

11. A stabilized motor fuel system as defined by claim 9, wherein the acid reacting substance is phosphoric acid.

12. A stabilized motor fuel storage system wherein the acid reacting substance is lactic acid.

WILLARD E. LYONS. 

